Chinese Chemical Letters 30 (2019) 1315–1319

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Chinese Chemical Letters

journal homepage: www.elsevier.com/locate/cclet

Communication

Effect of removing silica in rice husk for the preparation of activated

carbon for supercapacitor applications
Dechen Liua,1, Wenli Zhangb,1, Weimin Huangb,c,*
a
Jilin Police College, Changchun 130117, China
b
College of Chemistry, Jilin University, Changchun 130012, China
c
Key Laboratory of Physics and Technology for Advanced Batteries of Ministry of Education, Changchun 130012, China

A R T I C L E I N F O A B S T R A C T

Article history: Renewable biomass-derived activated carbons have attracted attentions for supercapacitor applications.
Received 22 January 2019 Rice husk is a kind of abundant biomass, which has been studied for the preparation of hierarchical
Received in revised form 25 January 2019 activated carbons. Rice husk is rich in silica. Silica in rice husk affects the formation of pore structure in
Accepted 25 January 2019
the KOH activation process, which further affects the electrochemical performance of the resultant
Available online 22 March 2019
activated carbon for supercapacitors. In this paper, the effects of silica in rice husk on the activation
process were investigated. When the silica in rice husk is not removed, KOH preferentially reacts with
Keywords:
silica to produce silicate, which hinders the formation and enlargement of mesopores; the obtained
Silica
Rice husk
activated carbon exhibits high microporous ratio, high specific area (up to 3263 m2/g), high specific
KOH activation capacitance (315 F/g at 0.5 A/g), but poor rate capability (51.7% capacitance retention with increasing the
Pore structure current density from 0.5 A/g to 20 A/g). When the silica in rice husk is removed, the pores produced by the
Supercapactiors removal of silica are etched to mesopores in activation process; the obtained activated carbon exhibits
high mesoporous ratio, relative high specific surface area of 2804 m2/g and relative high capacitance of
278 F/g at 0.5 A/g with excellent rate capability (76.6% capacitance retention with increasing the current
density from 0.5 A/g to 20 A/g).
© 2019 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.

In recent years, supercapacitors have attracted significant
attention, mainly due to their high power density, long cycling
life, and rapid charge/discharge processes. Activated carbon (AC) is
a promising electrode material for supercapacitors because of its
abundance, large surface area, relatively good electronic properties
and moderate cost [1–3]. Considering the production cost and
energy/environmental effects, the transformation of renewable
biomass to ACs is regarded as more worthwhile [4]. Until now, ACs
have been prepared from various renewable biomasses, such as
rice husk [5,6], cellulose [7–9] and lignin [10,11]. Among the above
biomasses, rice husk (RH) is a kind of low cost and abundant
biomass. The annual world rice production is about 571 million
tonnes, which produces approximately 140 million tonnes of
useless rice husk. Therefore, converting renewable rice husks into
electrode materials is supposed to be an economical and
sustainable route [4,12,13].
* Corresponding author at: College of Chemistry, Jilin University, Changchun
130012, China.
E-mail address: huangwm@jlu.edu.cn (W. Huang).
1
Authors with equal contributions.
RH contains a variety of organic components such as lignin,
cellulose, and hemicellulose. Besides, the unique composition
(silica) is formed during the growth of RH. It is known that silica
accounts for
15-20 wt% of the entire weight of RH [6]. In order to
obtain ACs with high specific surface area, KOH is often used as
activating agents. However, the silica in RH makes the activation
process of RH different from that of the other precursors. Namely,
silica in RH affects the formation of pores in activation process and
the electrochemical performances of the prepared AC. Although
some researches have reported the activation process of RH using
KOH as the activating agent, the effect of silica in RH on the
formation of pores during the activation process is not fully
understood.
In this paper, the effects of silica in rice husk on the activation
process and the electrochemical performances of the prepared AC
are investigated by removing the silica in rice husk by alkali
leaching (carbon materials denoted as RHCB) or not (carbon
material denoted as RHC) before activation process. When the
silica in RH is not removed, the prepared AC exhibits high specific
surface area, high micropore ratio, and high specific capacitance,
but poor rate capability. In the activation process, silica in RH
hinders the formation of mesopores. On the contrary, when the

https://doi.org/10.1016/j.cclet.2019.02.031
1001-8417/ © 2019 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
1316 D. Liu et al. / Chinese Chemical Letters 30 (2019) 1315–1319
Fig. 1. (a) EDS mapping of CRH with carbon, silicon and oxygen elements, (b) SEM and (c) TEM images of RHCB, (d) Nitrogen adsorption/desorption isotherms of RHC and
RHCB, (e) Pore size distributions of RHC and RHCB, (f) XRD patterns of KOH-impregnated CRH at 25  C, annealed at 400  C and 700  C for 1 h.
silica in RH is removed, the prepared AC exhibits high mesoporous
ratio and good rate capability.
Fig. 1a shows the typical energy dispersive spectroscopy (EDS)
mapping of carbonized rice husk (CRH). The silicon element exists
in the form of amorphous silica (account for ca. 45% of the weight of
CRH), as indicated by the consistent mapping of Si and O elements.
The RHCB shows apparent vascular bundle morphology in the
scanning electron microscopy (SEM) image (Fig. 1b), and RHCB
shows apparent micro/mesoporous structure inside carbon skele-
ton in the transmission electron microscopy (TEM) image (Fig. 1c).
However, it is hard to find the structural difference between RHC
and RHCB with SEM and TEM techniques. Therefore, it is important
to probe the porous structure of RHCB and RHC using N2
adsorption/desorption method. Fig. 1d shows N2 adsorption/
desorption isotherms of RHC and RHCB. The adsorption/desorption
isotherms of RHC are approximately type I isotherms according to
the IUPAC classification [14,15]. At relatively low pressure, the
adsorbed N2 volume increases steeply. At the higher relative
pressures, the adsorbed N2 volume rises to an almost horizontal
plateau. These results indicate that RHC possesses high micropo-
rosity. However, RHCB shows a combined I/IV type adsorption/
desorption isotherm (Fig. 1d). Strong N2 adsorption occurs at low
pressure due to the presence of micropores. The obvious hysteresis
loop between the adsorption and desorption branches suggests the
existence of mesopores. This adsorption behavior indicates that
the mesopores are significantly developed due to the removal of
silica in RH.
Shown in Fig. 1e are the pore size distributions of RHC and
RHCB. The RHC exhibits a narrow pore size distribution between
0.5 and 3 nm, indicating that large numbers of micropores exist in
RHC. This ensures a large specific surface area for RHC. On the
contrary, the pore sizes of the RHCB are distributed in a broad range
from 0.5 to 10 nm. There are several obvious peaks in Fig. 1e for
RHCB, which indicates the presence of micropores and mesopores
of different sizes. It can be concluded that the RHCB possesses a
combined micro/mesopore structure with a larger volume of
mesopores than RHC. The large volume mesopores of RHCB is
suitable for the mass transfer of electrolyte ions. As summarized in
Table S1 (see Supporting information), the specific surface area
(3263 m2/g) of RHC is larger than RHCB (2804 m2/g) due to the
presence of massive and large micropores in RHC. The micropore
volume of RHC reaches up to 1.132 cm3/g, which accounts for 63.9%
of the total volume. This confirms that the micropore is dominant
in RHC. On the contrary, the RHCB exhibits a low micropore volume
(0.476 cm3/g) accounting for 26.5% of the total volume. The
mesopore ratio is 73.5% for RHCB which is much higher than that of
RHC. From the above results, the RHC exhibits a high specific
surface area and high microporous ratio. On the contrary, the RHCB
exhibits high mesoporous ratio. This difference in pore size
distribution may be caused by the removal of silica or not during
activation process.
To investigate the effects of silica on the activation process, we
investigated the phases of rice husk reacted with KOH in the
calcination process. Fig. 1f shows the XRD patterns of KOH-
impregnated CRH at different temperatures. There is a broad
diffraction peak observed at 2u = 22.5 under 25  C, which is
attributed to amorphous silica in CRH. When the KOH-impregnat-
ed CRH was treated at 400  C, the broad peak of silica disappeared,
which is due to that silica reacts with KOH at 400  C. At the same
time, the peaks of K2CO3 were strengthened, which is due to the
reaction between CO2 produced in carbonization and KOH.
Namely, the silica reacts with KOH before 400  C, which precedes
the reaction of KOH with carbon. For the activation process of CRH,
the KOH preferentially reacts with silica in CRH generating the
new-born silicate before the reaction of carbon with KOH.
2KOH þ SiO2 ! K2 SiO3 þ 2H2 ð1Þ
The new-born silicate as a “shell” covers carbon, which hinders
the reaction of KOH with carbon. The metallic K and K2O are
produced during the further reaction. The metallic K intercalated
between the graphene layers of the carbon materials and
generated micropores. The KOH reacts with carbon may be as
 D. Liu et al. / Chinese Chemical Letters 30 (2019) 1315–1319
follows [16,17]:
4KOH þ C ! K2 CO3 þ K2 O þ 2H2
2KOH ! K2 O þ H2 O
K2 O þ CO2 ! K2 CO3
K2 O þ C ! 2K þ CO
K2 CO3 þ 2C ! 2K þ 3CO
To verify the above KOH-activation reactions, the activation
products from the activation process of CRH under 700  C were
analyzed by XRD. As shown in Fig. 1f, the peaks of KOH disappear.
The peaks of K2CO3, K, and K2O are dominant in XRD pattern. These
results prove the above reactions.
As for the activation process of CRHB (CRH treated with alkali
leaching), The CRHB exhibits higher specific area than CRH after
the removal of silica (Table S2 in Supporting information). The
specific surface area of the RHCB increases from 19 m2/g of CRH to
247 m2/g of CRHB with the removal of silica in CRH, similar with
the research published recently [4]. As can be seen, a large volume
of micropores and mesopores are formed due to the removal of
silica in CRH. The large volume of micropores and mesopores
results in a high mesopore ratio in RHCB. In the initial stage of the
activation process of CRHB, the reaction of silica with KOH do not
occur since almost all the silica are removed by NaOH leaching.
Because CRHB possesses relative high specific area, the KOH
congregates in the porous channel of nanostructured carbon in
CRHB via capillary effect. Along with the activation, the primary
porous micropores are enlarged to mesopores. And the already
formed mesopores are enlarged to larger mesopores. So the
resultant RHCB has higher mesoporous volume and larger
mesoporous size compared with RHC.
Fig. 2. The CV curves of (a) RHC and (b) RHCB; the GCD curves of (c) RHC and (d) RHCB.
1317
From the above discussion, the silica in RH plays an important
role in the activation process. The removal of silica is beneficial to
ð2Þ
form high pore volume and large size mesopores. In order to study
the difference in electrochemical performances of RHC and RHCB,
cyclic voltammetry (CV), galvanostatic charge-discharge (GCD),
ð3Þ
and electrochemical impedance spectroscopy (EIS) were carried
out in a 6 mol/L KOH aqueous electrolyte using a two-electrode
configuration.
ð4Þ
Figs. 2a and b show the CV curves of RHC and RHCB electrodes
at different scan rates from 5 mV/s to 1000 mV/s. The CV curves of
RHC and RHCB all exhibit quasi-rectangular shape indicating the
ð5Þ
ideal double-layer capacitive performances. Besides, the areas of
CV curves of RHC are higher than that of RHCB at low scan rates. So,
RHC has higher specific capacitance than RHCB. This is because
ð6Þ
RHC has a higher surface area than RHCB, which provides more
active sites for forming electric double layer by adsorption
electrolyte ions. This phenomenon becomes different with the
increase of scan rates. The CV curves of RHC are gradually distorted.
This is due to that the RHC possesses a large number of micropores,
which make ions transportation more difficult at a high scan rate.
However, the quasi-rectangular shapes of CV curves of RHCB are
still kept quasi-rectangular at 1000 mV/s. That is to say, the RHCB
exhibits a better rate capability compared with RHC. These results
are also verified by the GCD test. The GCD curves of RHC and RHCB
in a current range of 0.5–20 A/g in the voltage range between 0 and
1.0 V are shown in Figs. 2c and d. The symmetric GCD characteristic
with triangular shape typical for the ideal capacitor is observed.
The specific capacitances were calculated from the discharge
curves according to Eq. 7:
I Dt
Cg ¼ 4 ð7Þ
2mDu
Where I is the discharge current, m is the mass of one electrode, Dt
is the time change, Du is the voltage change. The specific
capacitances of the RHC and RHCB electrode at different current
densities were calculated according to GCD curves (Fig. 3a).
For the RHC electrode, the specific capacitance decreases from
315 F/g to 163 F/g as the current density increases from 0.5 A/g to
1318 D. Liu et al. / Chinese Chemical Letters 30 (2019) 1315–1319
Fig. 3. (a) The specific capacitances as a function of current density. The normalized real, the imaginary capacitances as a function of frequency for (b) RHC and (c) RHCB. (d)
Ragone plots of the symmetric supercapacitor.
20 A/g, with capacitance retention of ca. 51.7%. This poor rate
performance of RHC electrode is ascribed to its large diffusion
resistance in the micropores. It is worth noting that, RHCB
electrodes retains a high capacitance at the current density of
20 A/g compared with RHC. The specific capacitance of RHCB
electrode is 278 and 213 F/g at 0.5 and 20 A/g, respectively. About
76.6% of specific capacitance is retained when the GCD current
changes from 0.5 A/g to 20 A/g. The improved rate capability of
RHCB is attributed to the much more mesoporous structure
compared with RHC, enabling higher availability of electrolyte ions
at a high rate.
EIS is a nondestructive technique for understanding the
electrochemical behavior and providing complementary informa-
tion about the frequency response of the porous carbon electrode
[18]. The impedance frequency behavior was investigated by the
complex model of the capacitance (C (w)). It is well known that C
(w) is dependent on real capacitance C’(w), the imaginary
capacitance C”(w) related to the losses of energy dissipation and
frequency, which is defined as follows:
0 00
C ¼ C ðwÞ  jC ðwÞ
Z 00 ðwÞ
C 0 ðwÞ ¼ 2
wjZðwÞj
Z 0 ðwÞ
C 00 ðwÞ ¼
wjZðwÞj2
where Z’(w) and Z”(w) are the real and imaginary parts of the
complex impedance Z(w). w is the angular frequency which is
given by w = 2pf. The normalized C’(w) and C”(w) as a function of
frequency for the RHC and RHCB electrodes are presented in
Figs. 3b and c. It is obvious that the C’(w) gradually decreases with
the increase of frequency for both electrodes, however, the
capacitance of the RHCB electrode deteriorates more slowly than
that of RHC electrode, which can be attributed to the fast ion
diffusion and transport in the RHCB electrode. Besides, the
characteristic relaxation time constant defined as t 0 = 1/fo (t o,
the minimum time needed with an efficiency of greater than 50%)
is obtained from the frequency (fo) of C”(w) at the maximum value.
The fo is 2.51 Hz for the RHCB (Eqs. (8)–(10)), corresponding to the
t o = 398 ms, which is much lower than that of RHC electrode
(t o = 1002 ms, as shown in Figs. 3b and c) and other porous carbons
[19,20]. This result further demonstrates the fast accessibility of
the RHCB electrode to the electrolyte ions and excellent rate
capability at high scan rates with high power density character-
istics. It indicates that the RHCB presents superior rate capability,
in agreement with the results of CV and GCD test.
The energy density and the power density are important
parameters to characterize the electrochemical performances of
supercapacitor. Fig. 3d shows the Ragone plots of the symmetric
supercapacitors based on the RHC and RHCB electrodes. The
energy density and power density are calculated based on the
following equations:
C T DV 2
E¼ ð11Þ
2
ð8Þ
E
P¼ ð12Þ
ð9Þ t
where CT is the specific capacitance of the symmetric super-
capacitor based on the total masses of two electrodes, DV is the
voltage range (V) and t is the discharge time (s).
ð10Þ As shown in Fig. 3d, with the increase of power density, the
energy density of RHCB decreases slowly. When the power density
increases from 125 W/kg to 6195 W/kg, the energy density
decreases from 9.6 Wh/kg to 7.4 Wh/kg. However, the energy
density of RHC fast decreases to 5.6 Wh/kg with the increase of
power density, although the RHC shows a high energy density (as
high as 10.9 Wh/kg). It can be concluded that RHCB electrode is
capable of delivering high power without profound loss in energy,
indicating a promising application in high power electrochemical
capacitors [18]. On the contrary, the RHC electrode is suitable for
high energy electrochemical capacitors.
 D. Liu et al. / Chinese Chemical Letters 30 (2019) 1315–1319
From above results, RHC exhibits higher specific capacitance
compared with RHCB. However, the RHC exhibits poorer rate
capability compared with RHCB. Both RHC and RHCB show
excellent performances compared with the activated carbon
materials developed recently (Table S3 in Supporting information).
The different electrochemical performances of two electrode
materials are closely related to pore structure determined by the
presence or absence of silica during KOH activation process.
In this paper, the rice husk based-activated carbons were
prepared via KOH activation. The effects of the silica in RH in the
activation process on pore structure and electrochemical perfor-
mance of activated carbon are investigated by the removal of silica
with NaOH or not before activation. When silica in RH is not
removed, the silica preferentially reacts with KOH to product
silicate. The new-born silicate, as a “shell”, covers carbon, which
hinders the reaction of KOH with carbon and the enlargement of
pores. So, a large number of micropores are generated instead of
the development of mesopores. This endows the RHC with a high
specific area (as high as 3263 m2/g) but low mesoporous ratio
(36.1%), which leads to the high specific capacitance (315 F/g at
0.5 A/g), high energy density (10.9 Wh/kg), but poor rate ability.
When silica “template” in RH is removed, a large amount of pores
are formed. In the initial stage of activation, the activating agent
preferentially congregates in these pores, where these pores are
enlarged to larger mesopores along with activation. This gives the
RHCB with high mesopores ratio (73.5%). So, the RHCB exhibits
excellent rate capability with capacitance retention of 77% when
the current density is increased from 0.5 A/g to 20 A/g. In summary,
by removing the silica in RH before the activation process, a porous
carbon with a large mesoporous ratio and high rate capability can
be obtained. Further work will be carried out to design
pseudocapacitor using RHCB as supporting materials to replace
the extensively used graphene oxide (GO) [21,22].
Acknowledgments
The financial support from the National Key Research and
Development Program (No. 2016YFC1102802), National Natural
1319
Science Foundation of China (No. 21273097), the Science and
Technology Development Project of Jilin Province of China (No.
20130204003GX), the Thirteen Fifth Science and Technology
Project of the Ministry of Education of Jilin Province (No.
JJKH20181293KJ), and the Graduate Innovation Fund of Jilin
University (No. 2015141) are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.
cclet.2019.02.031.
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